WO2017086395A1 - シート、発熱体、及び発熱装置 - Google Patents
シート、発熱体、及び発熱装置 Download PDFInfo
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- WO2017086395A1 WO2017086395A1 PCT/JP2016/084145 JP2016084145W WO2017086395A1 WO 2017086395 A1 WO2017086395 A1 WO 2017086395A1 JP 2016084145 W JP2016084145 W JP 2016084145W WO 2017086395 A1 WO2017086395 A1 WO 2017086395A1
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- B32B2605/006—Transparent parts other than made from inorganic glass, e.g. polycarbonate glazings
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B30/00—Energy efficient heating, ventilation or air conditioning [HVAC]
Definitions
- the present invention relates to a sheet, a heating element, and a heating device.
- a method for producing a linear body containing carbon nanotubes for example, a linear body such as a ribbon or a thread
- a carbon nanotube forest is grown on the surface of a substrate by a chemical vapor deposition method (CVD: Chemical Vapor Deposition).
- a conductive linear body represented by a linear body containing carbon nanotubes (a linear body having a volume resistivity R of 1.0 ⁇ 10 ⁇ 7 ⁇ cm to 1.0 ⁇ 10 ⁇ 1 ⁇ cm) is, for example, It can be used as a light, thin, and high-strength wire, but if bundled into a pseudo-sheet structure, it may be used for various sheet-like products.
- a heating element of a heat generating device a material of a textile that generates heat
- a protective film for display a protective film for display (crush prevention film).
- the light transmittance of the heating element may be required.
- these sheet-like products are required to have low sheet resistance in order to reduce applied voltage in addition to light transmittance.
- ⁇ 1> A pseudo in which a volume resistivity R is 1.0 ⁇ 10 ⁇ 7 ⁇ cm to 1.0 ⁇ 10 ⁇ 1 ⁇ cm, and a plurality of linear bodies extending in one direction are arranged in parallel to each other at intervals.
- a sheet structure The relationship between the diameter D of the linear body and the distance L between the adjacent linear bodies satisfies the formula: L / D ⁇ 3, And the relationship between the volume resistivity R of the linear body and the interval L of the linear body adjacent to the diameter D of said linear body, wherein: (D 2 / R) ⁇ (1 / L) ⁇ 0 A sheet satisfying .003.
- ⁇ 2> The sheet according to ⁇ 1>, wherein the linear body is a linear body including carbon nanotubes.
- the linear body is a linear body containing carbon nanotubes and having a diameter of 1 ⁇ m to 125 ⁇ m.
- the linear body is a linear body including a carbon nanotube and a metal.
- ⁇ 5> The sheet according to any one of ⁇ 1> to ⁇ 4>, having an adhesive layer on which the pseudo sheet structure is laminated.
- ⁇ 6> The sheet according to any one of ⁇ 1> to ⁇ 5>, having a laminate in which a plurality of the pseudo sheet structures are stacked.
- the pseudo sheet structure has at least ends of the plurality of linear bodies fixed by a fixing member, and is in contact with other members other than the ends of the plurality of linear bodies fixed.
- a heating element comprising the sheet according to any one of ⁇ 1> to ⁇ 7>.
- ⁇ 9> A heat generating device including the heat generating element according to ⁇ 8> and a power supply unit that supplies power to the heat generating element.
- ⁇ 11> The heat generating device according to ⁇ 9>, which is a deicer.
- a sheet having a pseudo sheet structure that has high light transmittance and low surface resistance.
- a heating element that has high light transmittance and that can reduce the voltage to be applied, and a heating device that includes the heating element.
- a numerical range using “to” means a numerical range in which the numerical values shown before and after “to” are included as the minimum value and the maximum value, respectively.
- the sheet 10 includes, for example, a pseudo sheet structure 20 and an adhesive layer 30. Specifically, for example, in the sheet 10, the pseudo sheet structure 20 is laminated on the adhesive layer 30.
- 20A indicates one surface (hereinafter referred to as “first surface 20A”) of the pseudo sheet structure 20 on the side opposite to the surface on which the adhesive layer 30 is laminated.
- 20B shows the other surface (hereinafter referred to as “second surface 20B”) of the pseudo sheet structure 20 on which the adhesive layer 30 is laminated (see FIG. 2).
- 30A indicates one surface of the adhesive layer 30 on which the pseudo sheet structure 20 is laminated (hereinafter referred to as “first adhesive surface 30A”).
- 30B shows the other surface (hereinafter referred to as “second adhesive surface 30B”) of the adhesive layer 30 opposite to the surface on which the pseudo sheet structure 20 is laminated (see FIG. 2).
- the second sheet 20B of the pseudo sheet structure 20 and the first adhesive surface 30A of the adhesive layer 30 face each other, and the pseudo sheet structure 20 and the adhesive layer 30 are formed. They are stacked on each other.
- the pseudo sheet structure 20 has a volume resistivity R of 1.0 ⁇ 10 ⁇ 7 ⁇ cm to 1.0 ⁇ 10 ⁇ 1 ⁇ cm and a plurality of linear bodies 22 (hereinafter referred to as “conductive”) extending in one direction. Are also arranged in parallel with each other at intervals. Specifically, for example, in the pseudo sheet structure 20, a plurality of linear conductive wires 22 are arranged at equal intervals in a direction orthogonal to the length direction of the conductive wire 22. It has a structure. That is, the pseudo sheet structure 20 has, for example, a structure in which the conductive linear bodies 22 are arranged in a stripe shape.
- the relationship between the diameter D of the conductive linear body 22 and the interval L between the adjacent conductive linear bodies 22 satisfies the formula: L / D ⁇ 3, and the conductive linear body
- the relationship between the distance L between the adjacent conductive linear bodies 22 and the volume resistivity R of the conductive linear bodies 22 is expressed by the formula: (D 2 / R) ⁇ (1 / L) ⁇ 0. .003 is satisfied.
- the unit of D and L is cm.
- the volume resistivity R of the conductive linear body 22 is 1.0 ⁇ 10 ⁇ 7 ⁇ cm to 1.0 ⁇ 10 ⁇ 1 ⁇ cm, and 1.0 ⁇ 10 ⁇ 6 ⁇ cm to 1.0 ⁇ 10 ⁇ 1 ⁇ cm. 1.0 ⁇ 10 ⁇ 6 ⁇ cm to 1.0 ⁇ 10 ⁇ 2 ⁇ cm is more preferable, and 1.0 ⁇ 10 ⁇ 6 ⁇ cm to 4.0 ⁇ 10 ⁇ 5 ⁇ cm is even more preferable.
- the measurement of the volume resistivity R of the conductive linear body 22 is as follows.
- the diameter D of the conductive linear body 22 is obtained according to a method described later.
- a silver paste is applied to both ends of the conductive linear body 22 and the resistance of a portion having a length of 40 mm is measured to determine the resistance value of the conductive linear body 22.
- the cross-sectional area of the conductive linear body 22 is calculated, and this is multiplied by the measured length to obtain a volume.
- the obtained resistance value is divided by this volume to calculate the volume resistivity R of the conductive linear body 22.
- the diameter D of the conductive linear body 22 is preferably 0.0001 cm (1 ⁇ m) to 0.0125 cm (125 ⁇ m).
- the diameter of the conductive linear body 22 is preferably 0.0003 cm (3 ⁇ m) to 0.0100 cm (100 ⁇ m). More preferably, the thickness is from 0005 cm (5 ⁇ m) to 0.007 cm (70 ⁇ m), more preferably from 0.0005 cm (5 ⁇ m) to 0.004 cm (40 ⁇ m), and from 0.0005 cm (5 ⁇ m) to 0.002 cm (20 ⁇ m). ) Is most preferred.
- the conductive linear body 22 is a linear body including carbon nanotubes
- the diameter of the conductive linear body 22 is 1 ⁇ m to 125 ⁇ m
- the sheet 10 is manufactured. It is suppressed that the conductive linear body 22 is cut.
- the light transmittance of the sheet 10 (pseudo sheet structure 20) is improved. Thereby, for example, an image on the opposite side to the observer (a mirror image reflected in the case of a mirror) can be easily recognized via the sheet 10.
- the sheet 10 is attached to a window, it is easy to see a scene on the opposite side of the window.
- a linear body having a small diameter it is almost impossible to visually recognize the pseudo sheet structure 20 in the sheet 10 and an image through a window or a mirror can be visually recognized more naturally.
- the diameter D of the conductive linear body 22 is determined by observing the conductive linear body 22 of the pseudo sheet structure 20 using a digital microscope, and the diameter of the conductive linear body 22 at five randomly selected locations. And measure the average value.
- the interval L between the conductive linear bodies 22 is preferably 0.005 cm (50 ⁇ m) to 0.8 cm (8000 ⁇ m), and more preferably 0.008 cm (80 ⁇ m) to 0.65 cm (6500 ⁇ m).
- the distance L between the conductive linear bodies 22 is set to 0.005 cm (50 ⁇ m) to 0.8 cm (8000 ⁇ m)
- the light transmittance is easily improved while reducing the surface resistance of the pseudo sheet structure 20.
- the distance L between the conductive linear bodies 22 is determined by observing the conductive linear bodies 22 of the pseudo sheet structure 20 using a digital microscope and measuring the distance between the two adjacent conductive linear bodies 22.
- interval of two adjacent conductive linear bodies 22 is the length along the direction which arranged the conductive linear bodies 22, and the two conductive linear bodies 22 oppose each other. It is the length between the parts (see FIG. 2).
- the interval L is an average value of intervals between all adjacent conductive linear bodies 22 when the arrangement of the conductive linear bodies 22 is unequal, but the value of the interval L can be easily controlled. From the viewpoint of ensuring the uniformity of light transmittance, the conductive linear bodies 22 are preferably arranged at substantially equal intervals in the pseudo sheet structure 20.
- the conductive linear body 22 is not particularly limited as long as it has a volume resistivity in the above range, but may be a linear body containing carbon nanotubes (hereinafter also referred to as “carbon nanotube linear body”). Good. Since carbon nanotubes have higher thermal conductivity and higher electrical conductivity than various metals, applying a carbon nanotube linear body as the conductive linear body 22 reduces the surface resistance of the pseudo sheet structure 20 while reducing the surface resistance. The permeability is easily improved. Further, when the sheet 10 (pseudo sheet structure 20) is applied as a heating element, rapid heat generation is easily realized. Furthermore, it is easy to obtain a linear body having a small diameter as described above.
- the carbon nanotube linear body is, for example, a carbon nanotube forest (a growth body in which a plurality of carbon nanotubes are grown on a substrate so as to be oriented in a direction perpendicular to the substrate, and is called an “array”.
- the carbon nanotubes are drawn out in the form of a sheet from the end of the carbon nanotube sheet, the bundled carbon nanotube sheets are bundled, and then the bundle of carbon nanotubes is twisted.
- a ribbon-like carbon nanotube linear body is obtained when twisting is not applied during twisting, and a thread-like linear body is obtained when twisting is applied.
- the ribbon-like carbon nanotube linear body is a linear body having no structure in which the carbon nanotubes are twisted.
- a carbon nanotube linear body can be obtained by spinning from a carbon nanotube dispersion.
- the production of the carbon nanotube linear body by spinning can be performed by, for example, a method disclosed in US Publication No. 2013/0251619 (Japanese Unexamined Patent Publication No. 2011-253140).
- a filamentous carbon nanotube linear body From the viewpoint of obtaining a uniform diameter of the carbon nanotube linear body, it is desirable to use a filamentous carbon nanotube linear body.
- the carbon nanotube sheet is twisted. It is preferable to obtain a filamentous carbon nanotube linear body.
- the carbon nanotube linear body may be a linear body in which two or more carbon nanotube linear bodies are knitted together.
- the conductive linear body 22 may be a linear body including a carbon nanotube and a metal (hereinafter also referred to as “composite linear body”) in addition to the carbon nanotube linear body.
- composite linear body easily improves the conductivity of the linear body while maintaining the above-described characteristics of the carbon nanotube linear body. That is, it becomes easy to reduce the resistance of the pseudo sheet structure 20.
- the composite linear body for example, (1) a carbon nanotube linear body in which carbon nanotubes are drawn out from the end of a carbon nanotube forest into a sheet shape, the carbon nanotube sheets pulled out are bundled, and then a bundle of carbon nanotubes is twisted In the process of obtaining the composite linear body in which a single metal or a metal alloy is supported on the surface of a carbon nanotube forest, sheet or bundle, or a twisted linear body by vapor deposition, ion plating, sputtering, wet plating, etc.
- a metal when twisting a bundle of carbon nanotubes, a metal may be supported on the carbon nanotubes as in the composite linear body of (1).
- the composite linear body of (3) is a composite linear body when two linear bodies are knitted, but at least one linear body of metal or a linear body of metal alloy or composite If a linear body is included, three or more carbon nanotube linear bodies, a single metal linear body, a metal alloy linear body, or a composite linear body may be knitted.
- the metal of the composite linear body examples include simple metals such as gold, silver, copper, iron, aluminum, nickel, chromium, tin, and zinc, and alloys containing at least one of these metals (copper-nickel-phosphorus alloys, Copper-iron-phosphorus-zinc alloy).
- the conductive linear body 22 may be a linear body including a metal wire.
- the linear body including the metal wire may be a linear body composed of one metal wire, or may be a linear body obtained by twisting a plurality of metal wires.
- Metal wires include copper, aluminum, tungsten, iron, molybdenum, nickel, titanium, silver, gold and other metals, or alloys containing two or more metals (for example, steels such as stainless steel and carbon steel, brass, phosphorus Bronze, zirconium copper alloy, beryllium copper, iron nickel, nichrome, nickel titanium, cantal, hastelloy, rhenium tungsten, etc.).
- the metal wire may be plated with tin, zinc, silver, nickel, chromium, nickel-chromium alloy, solder, or the like, or may be one whose surface is coated with a carbon material or polymer described later. .
- a wire containing one or more metals selected from tungsten and molybdenum and alloys containing them is preferable from the viewpoint of forming the conductive linear body 22 having a low volume resistivity.
- An example of the metal wire is a metal wire coated with a carbon material. When the metal wire is coated with the carbon material, the metallic luster is reduced, and it becomes easy to make the presence of the metal wire inconspicuous. Further, when the metal wire is coated with a carbon material, metal corrosion is also suppressed.
- the carbon material covering the metal wire include amorphous carbon such as carbon black, activated carbon, hard carbon, soft carbon, mesoporous carbon, and carbon fiber; graphite; fullerene; graphene; carbon nanotube.
- the adhesive layer 30 is a layer containing an adhesive.
- the adhesive layer 30 makes it easy to attach the sheet 10 to an adherend.
- the adhesive layer 30 is a layer provided as necessary.
- the sheet 10 can be bonded to the adherend with the first surface 20A facing the adherend. In this case, as described above, in the sheet 10, the adhesion between the sheet 10 and the adherend is facilitated by the first adhesive surface 30 ⁇ / b> A of the adhesive layer 30 exposed from the pseudo sheet structure 20.
- the sheet 10 may be bonded to the adherend with the second adhesive surface 30B facing the adherend.
- the adhesive layer 30 is preferably curable. When the adhesive layer is cured, the adhesive layer 30 has sufficient hardness to protect the pseudo sheet structure 20, and the adhesive layer 30 also functions as a protective film. Moreover, the impact resistance of the adhesive layer 30 after curing is improved, and deformation of the adhesive layer 30 after curing due to impact can be suppressed.
- the adhesive layer 30 is preferably energy ray curable such as ultraviolet rays, visible energy rays, infrared rays, and electron beams in that it can be easily cured in a short time.
- the “energy ray curing” includes thermal curing by heating using energy rays.
- the curing conditions with energy rays vary depending on the energy rays to be used. For example, in the case of curing by ultraviolet irradiation, the irradiation amount of ultraviolet rays is 10 mJ / cm 2 to 3,000 mJ / cm 2 , and the irradiation time is 1 second to 180 seconds. It is preferable that
- Examples of the adhesive of the adhesive layer 30 include a so-called heat seal type adhesive that is bonded by heat, an adhesive that is moistened to express adhesiveness, and the like.
- a pressure-sensitive adhesive layer formed from an agent (pressure-sensitive adhesive) is preferable.
- the pressure-sensitive adhesive of the pressure-sensitive adhesive layer is not particularly limited.
- examples of the pressure-sensitive adhesive include acrylic pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, rubber-based pressure-sensitive adhesives, polyester-based pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, and polyvinyl ether-based pressure-sensitive adhesives.
- the adhesive is preferably at least one selected from the group consisting of an acrylic adhesive, a urethane adhesive, and a rubber adhesive, and more preferably an acrylic adhesive.
- acrylic pressure-sensitive adhesive examples include a polymer containing a structural unit derived from an alkyl (meth) acrylate having a linear alkyl group or a branched alkyl group (that is, a polymer obtained by polymerizing at least an alkyl (meth) acrylate) ), An acrylic polymer containing a structural unit derived from a (meth) acrylate having a cyclic structure (that is, a polymer obtained by polymerizing at least a (meth) acrylate having a cyclic structure) and the like.
- (meth) acrylate” is used as a term indicating both “acrylate” and “methacrylate”, and the same applies to other similar terms.
- the acrylic polymer is a copolymer
- the form of copolymerization is not particularly limited.
- any of a block copolymer, a random copolymer, or a graft copolymer may be sufficient.
- the acrylic pressure-sensitive adhesive is derived from an alkyl (meth) acrylate (a1 ′) having a chain alkyl group having 1 to 20 carbon atoms (hereinafter also referred to as “monomer component (a1 ′)”).
- the acrylic copolymer containing the structural unit (a2) derived from the structural unit (a1) and the functional group-containing monomer (a2 ′) (hereinafter also referred to as “monomer component (a2 ′)”) is preferable.
- the acrylic copolymer further includes a structural unit (a3) derived from the monomer component (a3 ′) other than the monomer component (a1 ′) and the monomer component (a2 ′). You may go out.
- the number of carbon atoms of the chain alkyl group possessed by the monomer component (a1 ′) is preferably 1 to 12, more preferably 4 to 8, and further preferably 4 to 6, from the viewpoint of improving the adhesive properties.
- the monomer component (a1 ′) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) ) Acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate and the like.
- butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are preferable, and butyl (meth) acrylate is more preferable.
- the content of the structural unit (a1) is preferably 50% by mass to 99.5% by mass, more preferably 55% by mass to 99% by mass with respect to the total structural unit (100% by mass) of the acrylic copolymer. %, More preferably 60% by mass to 97% by mass, and still more preferably 65% by mass to 95% by mass.
- Examples of the monomer component (a2 ′) include a hydroxy group-containing monomer, a carboxy group-containing monomer, an epoxy group-containing monomer, an amino group-containing monomer, a cyano group-containing monomer, a keto group-containing monomer, and an alkoxysilyl group-containing monomer. Can be mentioned. Among these monomer components (a2 ′), a hydroxy group-containing monomer and a carboxy group-containing monomer are preferable.
- Examples of the hydroxy group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl ( (Meth) acrylate and the like, and 2-hydroxyethyl (meth) acrylate is preferable.
- Examples of the carboxy group-containing monomer include (meth) acrylic acid, maleic acid, fumaric acid, and itaconic acid, and (meth) acrylic acid is preferable.
- Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate.
- Examples of the amino group-containing monomer include diaminoethyl (meth) acrylate.
- Examples of the cyano group-containing monomer include acrylonitrile.
- the content of the structural unit (a2) is preferably 0.1% by mass to 50% by mass, more preferably 0.5% by mass to the total structural unit (100% by mass) of the acrylic copolymer. It is 40% by mass, more preferably 1.0% by mass to 30% by mass, and still more preferably 1.5% by mass to 20% by mass.
- Examples of the monomer component (a3 ′) include cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and dicyclohexane.
- Examples thereof include (meth) acrylates having a cyclic structure such as pentenyloxyethyl (meth) acrylate, imide (meth) acrylate, and acryloylmorpholine; vinyl acetate; styrene.
- the content of the structural unit (a3) is preferably 0% by mass to 40% by mass, more preferably 0% by mass to 30% by mass, with respect to the total structural unit (100% by mass) of the acrylic copolymer. More preferably, it is 0% by mass to 25% by mass, and still more preferably 0% by mass to 20% by mass.
- the above-mentioned monomer component (a1 ′) may be used alone or in combination of two or more, and the above-mentioned monomer component (a2 ′) is used alone or in combination of two or more.
- the monomer component (a3 ′) described above may be used alone or in combination of two or more.
- the acrylic copolymer may be crosslinked with a crosslinking agent.
- the crosslinking agent include known epoxy crosslinking agents, isocyanate crosslinking agents, aziridine crosslinking agents, metal chelate crosslinking agents, and the like.
- the functional group derived from the monomer component (a2 ′) can be used as a cross-linking point that reacts with the cross-linking agent.
- the pressure-sensitive adhesive layer may contain an energy ray-curable component in addition to the pressure-sensitive adhesive.
- an energy ray-curable component for example, when the energy ray is ultraviolet ray, for example, trimethylolpropane tri (meth) acrylate, ethoxylated isocyanuric acid tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, Tetramethylolmethane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, 1, 4-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, di
- an acrylic pressure-sensitive adhesive When an acrylic pressure-sensitive adhesive is applied as the pressure-sensitive adhesive, a functional group that reacts with a functional group derived from the monomer component (a2 ′) in the acrylic copolymer as an energy ray-curable component, and an energy ray A compound having a polymerizable functional group in one molecule may be used. Due to the reaction between the functional group of the compound and the functional group derived from the monomer component (a2 ′) in the acrylic copolymer, the side chain of the acrylic copolymer can be polymerized by irradiation with energy rays. Even if the pressure-sensitive adhesive is other than an acrylic pressure-sensitive adhesive, a component having a side chain that is energy ray polymerizable may be used as a copolymer component other than the copolymer that becomes the pressure-sensitive adhesive.
- the pressure-sensitive adhesive layer When the pressure-sensitive adhesive layer is energy ray curable, the pressure-sensitive adhesive layer preferably contains a photopolymerization initiator.
- the speed at which the pressure-sensitive adhesive layer is cured by irradiation with energy rays can be increased by the photopolymerization initiator.
- the photopolymerization initiator include benzophenone, acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate, benzoin dimethyl ketal, 2,4-diethylthioxanthone.
- the pressure-sensitive adhesive layer may contain an inorganic filler.
- the hardness of the pressure-sensitive adhesive layer after curing can be further improved.
- the thermal conductivity of the pressure-sensitive adhesive layer is improved.
- the adherend is mainly composed of glass, the linear expansion coefficient of the sheet 10 and the adherend can be made closer, whereby the sheet 10 is stuck to the adherend and cured as necessary. The reliability of the obtained device is improved.
- the inorganic filler examples include powders of silica, alumina, talc, calcium carbonate, titanium white, bengara, silicon carbide, boron nitride, and the like; beads formed by spheroidizing these; single crystal fibers; glass fibers, and the like.
- a silica filler and an alumina filler are preferable.
- An inorganic filler may be used individually by 1 type, and may use 2 or more types together.
- the inorganic filler is preferably surface-modified (coupled) with a compound having a curable functional group.
- the curable functional group include a hydroxyl group, a carboxyl group, an amino group, a glycidyl group, an epoxy group, an ether group, an ester group, and a group having an ethylenically unsaturated bond.
- the compound having a curable functional group include a silane coupling agent.
- the inorganic filler has an energy ray-curable functional group such as a group having an ethylenically unsaturated bond from the viewpoint that the fracture resistance of the adhesive layer after curing (strength of the adhesive layer after curing) is easily maintained. More preferably, the surface is modified with a compound.
- the group having an ethylenically unsaturated bond include a vinyl group, a (meth) acryloyl group, and a maleimide group, and a (meth) acryloyl group is preferable from the viewpoint of high reactivity and versatility.
- the inorganic filler is surface-modified with a compound having an energy ray-curable functional group, for example, the pressure-sensitive adhesive layer cured after the sheet 10 is attached to an adherend such as glass becomes tough. Thereby, it becomes easy to avoid destruction of the cured adhesive layer when the suction cup is attached to the sheet 10 attached to a window, a mirror or the like and the sheet 10 is peeled off.
- the adhesive layer contains the energy-beam curable component separately.
- the average particle size of the inorganic filler is preferably 1 ⁇ m or less, and more preferably 0.5 ⁇ m or less. If the average particle size of the inorganic filler is in such a range, the light transmittance of the sheet 10 (that is, the pressure-sensitive adhesive layer) is easily improved, and the haze of the sheet 10 (that is, the pressure-sensitive adhesive layer) is easily reduced. can do.
- the minimum of the average particle diameter of an inorganic filler is not specifically limited, It is preferable that it is 5 nm or more.
- the average particle diameter of the inorganic filler is determined by observing 20 inorganic fillers with a digital microscope, measuring the average diameter of the maximum diameter and the minimum diameter of the inorganic filler as a diameter, and taking the average value.
- the content of the inorganic filler is preferably 0% by mass to 95% by mass, more preferably 5% by mass to 90% by mass with respect to the entire pressure-sensitive adhesive layer, and 10% by mass to 80% by mass. More preferably.
- the pencil hardness of the cured adhesive layer is preferably HB or higher, more preferably F or higher, and even more preferably H or higher. Thereby, the function in which the adhesive layer after hardening protects the pseudo sheet structure 20 further improves, and the pseudo sheet structure 20 can be more fully protected. Further, the pressure-sensitive adhesive layer is located farther from the adherend than the pseudo-sheet structure 20 and the surface of the pressure-sensitive adhesive layer opposite to the surface adjacent to the pseudo-sheet structure 20 (first adhesive surface 30A) ( Even when the support is not provided on the second adhesive surface 30B), it is easy to prevent the cured adhesive layer itself from being damaged after the sheet 10 is applied to the adherend. .
- the pencil hardness is a value measured according to JISK5600-5-4.
- the pressure-sensitive adhesive layer may contain other components.
- other components include well-known additives such as organic solvents, flame retardants, tackifiers, ultraviolet absorbers, antioxidants, antiseptics, antifungal agents, plasticizers, antifoaming agents, and wettability modifiers. Is mentioned.
- the thickness of the adhesive layer 30 is appropriately determined according to the use of the sheet 10.
- the thickness of the adhesive layer 30 is preferably 3 ⁇ m to 150 ⁇ m, and more preferably 5 ⁇ m to 100 ⁇ m.
- seat 10 which concerns on this embodiment is not specifically limited.
- the sheet 10 is manufactured through the following steps, for example. First, the composition for forming the adhesive layer 30 is applied on the release sheet to form a coating film. Next, the coating film is dried to produce the adhesive layer 30. Next, the pseudo linear sheet structure 20 is formed by arranging the conductive linear bodies 22 while arranging them on the first adhesive surface 30A of the adhesive layer 30. For example, the conductive linear body 22 is spirally formed on the first adhesive surface 30A of the adhesive layer 30 while rotating the drum member in a state where the adhesive layer 30 with the release sheet is disposed on the outer peripheral surface of the drum member. Wrap around.
- the bundle of conductive linear bodies 22 wound in a spiral shape is cut along the axial direction of the drum member.
- the pseudo sheet structure 20 is formed and disposed on the first adhesive surface 30 ⁇ / b> A of the adhesive layer 30.
- the adhesive layer 30 with the release sheet on which the pseudo sheet structure 20 is formed is taken out from the drum member.
- the release sheet is peeled from the adhesive layer 30 to obtain the sheet 10.
- the conductive portions adjacent to each other in the pseudo sheet structure 20 are moved by moving the feeding portion of the conductive linear body 22 along the direction parallel to the axis of the drum member. It is easy to adjust the distance L between the linear bodies 22.
- the second surface 20 ⁇ / b> B of the obtained pseudo sheet structure 20 is pasted on the first adhesive surface 30 ⁇ / b> A of the adhesive layer 30.
- the sheet 10 may be produced.
- the light transmittance of the sheet 10 is preferably 70% or more, more preferably 70% to 100%, and still more preferably 80% to 100%.
- the light transmittance of the sheet 10 is 70% or more, it is possible to easily obtain such visibility or contrast sharpness.
- the light transmittance of the sheet 10 is determined by measuring the light transmittance in the visible region (380 nm to 760 mm) with a light transmittance meter, and taking the average value.
- the sheet 10 is applied as a heating element, the sheet 10 having a low surface resistance is required from the viewpoint of reducing the applied voltage. If the sheet resistance of the sheet 10 is 800 ⁇ / ⁇ or less, the applied voltage can be easily reduced.
- the sheet resistance of the sheet 10 is measured by the following method. First, in order to improve electrical connection, a silver paste is applied to both ends of the pseudo sheet structure 10 of the sheet 10. Then, after affixing the sheet
- the sheet 10 according to the present embodiment is used by being attached to an adherend, for example.
- the adhesive layer 30 has curability, the adhesive layer 30 is cured after the sheet 10 is attached to the adherend.
- the pseudo sheet structure 20 side of the sheet 10 is attached to the adherend (that is, between the first adhesive surface 30A of the adhesive layer 30 and the adherend).
- the pseudo-sheet structure 20 may be interposed and attached to the adherend), or the second adhesive surface 30B of the sheet 10 may be attached to the adherend.
- the adhesive bond layer 30 contributes also to the electric shock prevention at the time of heat_generation
- the sheet 10 according to the present embodiment is not limited to the above form, and may be modified or improved.
- modified examples of the sheet 10 according to the present embodiment will be described.
- symbol is attached
- the sheet 10 includes a support 32 laminated on the first surface 20 ⁇ / b> A of the pseudo-sheet structure 20 or the second adhesive surface 30 ⁇ / b> B of the adhesive layer 30. You may do it.
- the support body 32 is laminated on the first surface 20 ⁇ / b> A of the pseudo sheet structure 20
- the support body 32 is fixed on the sheet 10 by the first adhesive surface 30 ⁇ / b> A of the adhesive layer 30 exposed from the pseudo sheet structure body 20.
- 3 shows the sheet 11 having the support 32 stacked on the second adhesive surface 30B of the adhesive layer 30.
- Examples of the support 32 include paper, a thermoplastic resin film, a cured film of a curable resin, a metal foil, and a glass film.
- examples of the thermoplastic resin film include polyester, polycarbonate, polyimide, polyolefin, polyurethane, and acrylic resin films.
- a hard coat treatment using an ultraviolet curable resin or the like may be performed.
- the sheet 10 includes, for example, a release layer 34 laminated on at least one of the first surface 20A of the pseudo sheet structure 20 and the second adhesive surface 30B of the adhesive layer 30. Also good. 4 shows the sheet 12 having the release layer 34 laminated on both the first surface 20A of the pseudo-sheet structure 20 and the second adhesive surface 30B of the adhesive layer 30. .
- the release layer 34 is not particularly limited.
- the release layer 34 preferably includes a release substrate and a release agent layer formed by applying a release agent on the release substrate.
- the release layer 34 may include a release agent layer only on one side of the release substrate, or may include a release agent layer on both sides of the release substrate.
- the release substrate include a paper substrate, a laminated paper obtained by laminating a thermoplastic resin (polyethylene, etc.) on a paper substrate, a plastic film, and the like.
- the paper substrate include glassine paper, coated paper, cast coated paper, and the like.
- plastic film examples include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyolefin films such as polypropylene and polyethylene.
- release agent examples include olefin resins, rubber elastomers (eg, butadiene resins, isoprene resins, etc.), long chain alkyl resins, alkyd resins, fluorine resins, silicone resins, and the like.
- the thickness of the release layer 34 is not particularly limited. Usually, the thickness of the release layer 34 is preferably 20 ⁇ m to 200 ⁇ m, and more preferably 25 ⁇ m to 150 ⁇ m.
- the thickness of the release agent layer of the release layer 34 is not particularly limited. When a release agent layer is formed by applying a solution containing a release agent, the thickness of the release agent layer is preferably 0.01 ⁇ m to 2.0 ⁇ m, and more preferably 0.03 ⁇ m to 1.0 ⁇ m. When a plastic film is used as the peeling substrate, the thickness of the plastic film is preferably 3 ⁇ m to 150 ⁇ m, and more preferably 5 ⁇ m to 100 ⁇ m.
- the sheet 10 according to the present embodiment may be a sheet 13 having another adhesive layer 31 laminated on the first surface 20 ⁇ / b> A of the pseudo sheet structure 20. That is, the sheet 10 according to the present embodiment may have an adhesive layer on both surfaces (the first surface 20A and the second surface 20B) of the pseudo sheet structure 20.
- the adhesive layer 30 and the adhesive layer 31 may have the same composition or different compositions.
- the thicknesses of the adhesive layer 30 and the adhesive layer 31 are each preferably 3 ⁇ m to 150 ⁇ m, and more preferably 5 ⁇ m to 100 ⁇ m.
- the total thickness of the adhesive layer 30 and the adhesive layer 31 is preferably 10 ⁇ m to 300 ⁇ m, and more preferably 20 ⁇ m to 200 ⁇ m.
- the sheet 10 according to the present embodiment is a sheet 14 having another adhesive layer 31 laminated on the second adhesive surface 30 ⁇ / b> B of the adhesive layer 30 via a support layer 36.
- the sheet 10 according to the present embodiment includes an adhesive sheet (such as a double-sided tape) including a pair of adhesive layers 30 and 31 laminated on the second surface 20B of the pseudo sheet structure 20 via the support layer 36.
- the support layer 36 include paper, a thermoplastic resin film, a cured film of a curable resin, a metal foil, and a glass film.
- the thermoplastic resin film include polyester, polycarbonate, polyimide, polyolefin, polyurethane, and acrylic resin films.
- the conductive linear body 22 of the pseudo sheet structure 20 may be periodically curved or bent.
- the conductive linear body 22 may have a wave shape such as a sine wave, a rectangular wave, a triangular wave, and a sawtooth wave.
- the pseudo sheet structure 20 has, for example, a structure in which a plurality of wavy conductive linear bodies 22 extending in one direction are arranged at equal intervals in a direction orthogonal to the extending direction of the conductive linear bodies 22.
- Also good. 7 includes a pseudo sheet structure 20 in which a plurality of wavy conductive linear bodies 22 extending in one direction are arranged at equal intervals in a direction orthogonal to the extending direction of the conductive linear bodies 22.
- a sheet 15 is shown.
- the sheet 10 may be a sheet having a stacked body in which a plurality of pseudo sheet structures 20 are stacked.
- the plurality of pseudo sheet structures 20 may be formed by stacking the conductive linear bodies 22 in parallel or crossing each other.
- the conductive linear bodies 22 that are arranged in parallel and do not intersect with each other are bridged by the conductive linear bodies 22 of the other pseudo sheet structure 20. From the viewpoint of achieving a good connection, it is preferable to laminate the conductive linear bodies 22 so as to cross each other.
- FIG. 8 shows a sheet 16 in which the two conductive sheet bodies 20 are stacked by crossing the conductive linear bodies 22 with each other.
- the sheet 10 may be a sheet in which a plurality of pseudo sheet structures 20 are arranged in the sheet surface direction (direction along the sheet surface).
- the conductive linear bodies 22 may be arranged in parallel, or may be arranged so as to intersect each other.
- FIG. 9 shows a sheet 17 in which the two conductive sheet structures 20 are arranged by arranging the conductive linear bodies 22 in parallel.
- the sheet 10 according to the present embodiment may have a form that does not include the adhesive layer 30.
- the pseudo sheet structure 20 has at least the ends of the plurality of conductive linear bodies 22 fixed by a fixing member, and other than the ends of the plurality of conductive linear bodies 22 fixed, The form which has the independent part which is not in contact with the other member may be sufficient.
- the sheet 10 is formed of a single-layer adhesive with an edge portion of the pseudo sheet structure 20 having a fixing member 38 (for example, a double-sided tape and no core material).
- a sheet 18 (free-standing sheet) composed of a pseudo-sheet structure 20 fixed by a double-sided adhesive film, solder, a heat-sealable film, a fixing member such as a clip or a pinch of a vise, etc. Also good.
- the edge part of the pseudo sheet structure 20 is not limited to the form fixed by the fixing member 38, and only a pair of opposing edge parts of the pseudo sheet structure 20 (only the end parts of the plurality of conductive linear bodies 22). May be fixed by the fixing member 38.
- the sheet 10 according to the present embodiment may be in a form in which the first to seventh modifications are combined.
- the sheet 10 according to the present embodiment has (1) a form having a support 32 laminated on the first surface 20A of the pseudo-sheet structure 20 in the second modified example having the release layer 34, (2) In the third modification, a form having a support 32 laminated on the surface of the other adhesive layer 31 (the surface not facing the pseudo sheet structure 20), (3) In the third modification, two adhesives (4) In the fourth modification, the first surface 20A of the pseudo sheet structure 20 is provided with a release layer laminated on at least one surface of the layers 30 and 31 (the surface not facing the pseudo sheet structure 20).
- stacked on top may be sufficient.
- the sheet 10 according to the present embodiment has a pseudo-sheet structure having high light transmittance and low surface resistance, it is preferable to apply as a heating element.
- the heating element made of the sheet 10 according to the present embodiment is a heating element having high light transmittance and capable of reducing the applied voltage.
- the heating device 40 includes a heating element 42 (a heating element formed of the sheet 10 according to the present embodiment) and a heating element 42 (a simulation thereof). And a power feeding section 44 that feeds power to the sheet structure 20).
- the power feeding unit 44 is made of, for example, a metal material, and is electrically connected to the end of the pseudo sheet structure 20 of the heating element 42 (sheet 10).
- the power feeding unit 44 and the pseudo sheet structure 20 are joined by a known method such as soldering so that power can be fed to each conductive linear body 22 of the pseudo sheet structure 20.
- the heating device 40 includes, for example, a mirror such as a bathroom; a window of a transportation device such as a passenger car, a railway, a ship, and an aircraft; a window of a building; a defogger arranged in eyewear and the like. , A window of a transportation device, a lighting surface of a traffic light, a deicer arranged on a sign or the like.
- Example 1 A carbon nanotube forest was obtained on a silicon wafer having a width of 50 mm by a catalytic CVD method using argon gas as a carrier gas, acetylene as a carbon source, and a thermal CVD (Chemical Vapor Deposition) apparatus having three furnaces as a vapor deposition apparatus. A part of the end of the carbon nanotube forest was pinched to pull out the carbon nanotube sheet with a width of 7 mm. The carbon nanotube sheet is passed through a metal ring having a diameter of 5 mm so that the sheets are bundled. The bundled sheets are put on a rubber drum having a diameter of 3 cm, and the rubber drum is vibrated in the axial direction of the drum to be bundled.
- Example 2 Example 1 except that a linear body made of a metal wire (metal type: Stainless Steel, product number: AISI 316L (Good fellow), diameter: 50 ⁇ m) was used instead of the carbon nanotube sheet linear body. Similarly, the sheet
- Example 3 A sheet in which a pseudo sheet structure in which carbon nanotube linear bodies are arranged is laminated on an adhesive sheet in the same manner as in Example 1 except that the linear body is wound by changing the moving speed of the rubber drum more slowly.
- the diameter D and the interval L of the linear bodies of the pseudo sheet structure were measured by the method described above, the diameter D of the linear bodies was 20 ⁇ m, and the interval L between the arranged linear bodies was 800 ⁇ m.
- Example 4 A sheet in which a pseudo sheet structure in which carbon nanotube linear bodies are arranged is laminated on an adhesive sheet in the same manner as in Example 1 except that the linear body is wound by changing the moving speed of the rubber drum more slowly. Got.
- the diameter D and the interval L of the linear bodies of the pseudo sheet structure were measured by the method described above, the diameter D of the linear bodies was 20 ⁇ m, and the interval L between the arranged linear bodies was 200 ⁇ m.
- Example 1 A sheet in which a pseudo sheet structure in which carbon nanotube linear bodies are arranged is laminated on an adhesive sheet in the same manner as in Example 1 except that the linear body is wound by changing the moving speed of the rubber drum more slowly. Got.
- the diameter D and the interval L of the linear bodies of the pseudo sheet structure were measured by the method described above, the diameter D of the linear bodies was 20 ⁇ m, and the interval L between the arranged linear bodies was 10 ⁇ m.
- Example 2 A sheet in which a pseudo sheet structure in which carbon nanotube linear bodies are arranged is laminated on an adhesive sheet in the same manner as in Example 1 except that the linear body is wound by changing the moving speed of the rubber drum faster. Got.
- the diameter D and the interval L of the linear bodies of the pseudo sheet structure were measured by the method described above, the diameter D of the linear bodies was 20 ⁇ m, and the interval L between the arranged linear bodies was 10000 ⁇ m.
- Example 5 In the same manner as in Example 1, except that the diameter of the linear body of the carbon nanotube sheet was changed to 15 ⁇ m instead of 20 ⁇ m, and the linear body was wound by changing the moving speed of the rubber drum more slowly, A sheet in which pseudo-sheet structures in which nanotube linear bodies are arranged was laminated was obtained.
- the diameter D and the interval L of the linear bodies of the pseudo sheet structure were measured by the method described above, the diameter D of the linear bodies was 15 ⁇ m, and the interval L between the arranged linear bodies was 100 ⁇ m.
- Example 6 Instead of the carbon nanotube sheet linear body, a linear body made of metal wire (metal type: Stainless Steel, product number: AISI 316L (Good fellows), diameter: 50 ⁇ m) is used, and the speed at which the rubber drum moves is increased.
- a sheet in which a pseudo sheet structure in which linear bodies made of metal wires are arranged on an adhesive sheet was laminated was obtained in the same manner as in Example 1 except that a linear body made of metal wires was wound around. .
- the diameter D and the distance L of the linear body of the pseudo sheet structure were measured by the above-described method. was 5000 ⁇ m.
- Example 7 Example 1 was used except that a linear body made of a metal wire (metal type: tungsten, product name: TGW-B (manufactured by Tokusai), diameter 14 ⁇ m) was used instead of the carbon nanotube sheet linear body. And the sheet
- the diameter D and the distance L of the linear body of the pseudo sheet structure were measured by the above-described method, the diameter D of the linear body made of metal wires was 14 ⁇ m, and the distance L between the linear bodies made of arranged metal wires. was 1700 ⁇ m.
- Example 8 Example 1 except that a linear body made of metal wire (metal type: molybdenum, product name: TMG-BS (manufactured by Tokusai Co., Ltd.), diameter 25 ⁇ m) was used instead of the carbon nanotube sheet linear body.
- a sheet was obtained in which a pseudo sheet structure in which linear bodies made of metal wires were arranged on an adhesive sheet was laminated.
- the diameter D and the distance L of the linear body made of the metal wire of the pseudo sheet structure were measured by the method described, the diameter D of the linear body made of the metal wire was 25 ⁇ m, and the linear body made of the arranged metal wires The distance L was 1700 ⁇ m.
- the sheet of this example is a sheet having a pseudo-sheet structure having higher light transmittance and lower surface resistance than the sheet of the comparative example.
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Abstract
Description
<1> 体積抵抗率Rが1.0×10-7Ωcm~1.0×10-1Ωcmであり、かつ一方向に延びた複数の線状体が、互いに平行に間隔をもって配列された疑似シート構造体を有し、
前記線状体の直径Dと隣り合う前記線状体の間隔Lとの関係が、式:L/D≧3を満たし、
かつ前記線状体の直径Dと隣り合う前記線状体同士の間隔Lと前記線状体の体積抵抗率Rとの関係が、式:(D2/R)×(1/L)≧0.003を満たすシート。
<2> 前記線状体が、カーボンナノチューブを含む線状体である<1>に記載のシート。
<3> 前記線状体が、カーボンナノチューブを含み、かつ直径が1μm~125μmの線状体である<1>又は<2>に記載のシート。
<4> 前記線状体が、カーボンナノチューブと金属とを含む線状体である<1>~<3>のいずれか1項に記載のシート。
<5> 前記疑似シート構造体が積層される接着剤層を有する<1>~<4>のいずれか1項に記載のシート。
<6> 前記疑似シート構造体が複数重ねられた積層体を有する<1>~<5>のいずれか1項に記載のシート。
<7> 前記疑似シート構造体が、少なくとも前記複数の線状体の端部が固定部材により固定され、かつ固定された前記複数の線状体の端部以外に、他の部材と接触していない独立した部分を有する<1>~<7>のいずれか1項に記載のシート。
<8> <1>~<7>のいずれか1項に記載のシートからなる発熱体。
<9> <8>に記載の発熱体と、前記発熱体に給電する給電部とを有する発熱装置。
<10> デフォッガーである<9>の発熱装置。
<11> デアイサーである<9>に記載の発熱装置。
本実施形態に係るシート10は、図1及び図2に示すように、例えば、疑似シート構造体20と、接着剤層30とを有している。具体的には、例えば、シート10は、接着剤層30上に疑似シート構造体20が積層されている。
疑似シート構造体20は、体積抵抗率Rが1.0×10-7Ωcm~1.0×10-1Ωcmであり、かつ一方向に延びた複数の線状体22(以下、「導電性線状体」とも称する)が、互いに平行に間隔をもって配列された構造としている。具体的には、例えば、疑似シート構造体20は、直線状に伸びた導電性線状体22が、導電性線状体22の長さ方向と直交する方向に、等間隔で複数配列された構造としている。つまり、疑似シート構造体20は、例えば、導電性線状体22がストライプ状に配列された構造としている。
なお、疑似シート構造体20の光線透過性及び面抵抗の点から、式:350≧L/D≧3を満たすことが好ましく、式:250≧L/D≧5を満たすことがより好ましい。また、同じ点から、式:20≧(D2/R)×(1/L)≧0.03を満たすことが好ましく、式:15≧(D2/R)×(1/L)≧0.5を満たすことがより好ましく、式:10≧(D2/R)×(1/L)≧3を満たすことがさらに好ましい。
なお、式:350≧L/D≧3を満たし、かつ式:7≧(D2/R)×(1/L)≧0.003を満たしても、式:250≧L/D≧5を満たし、かつ式:5≧(D2/R)×(1/L)≧0.004を満たしてもよい。
導電性線状体22の体積抵抗率Rの測定は、次の通りである。まず、後述する方法に従って、導電性線状体22の直径Dを求める。次に、導電性線状体22の両端に銀ペーストを塗布し、長さ40mmの部分の抵抗を測定し、導電性線状体22の抵抗値を求める。そして、直径Dの柱状の導電性線状体22と仮定して、導電性線状体22の断面積を算出し、これに上記の測定した長さを乗じて体積とする。得られた抵抗値を、この体積で除して、導電性線状体22の体積抵抗率Rを算出する。
特に、導電性線状体22がカーボンナノチューブを含む線状体である場合、導電性線状体22の直径を1μm~125μmにすると、シート10(疑似シート構造体20)の製造の際に、導電性線状体22が切れることが抑制される。また、導電性線状体22の一本一本が肉眼で視認し難くなるため、シート10(疑似シート構造体20)の光線透過性が向上する。これにより、例えば、シート10を介して、観察者に対して反対側にある映像(鏡であれば、反射された鏡像)が認識しやすくなる。具体的には、例えば、シート10を窓に貼付した際には、窓の反対側の光景が見やすくなる。また、直径が細い線状体を用いると、シート10における疑似シート構造体20を肉眼で視認することがほとんど不可能になり、窓や鏡を介した像をより自然に視認することができる。
なお、隣り合う2つの導電性線状体22の間隔とは、導電性線状体22を配列させていった方向に沿った長さであって、2つの導電性線状体22の対向する部分間の長さである(図2参照)。間隔Lは、導電性線状体22の配列が不等間隔である場合には、すべての隣り合う導電性線状体22同士の間隔の平均値であるが、間隔Lの値を制御しやすくする観点、光線透過性の均一性の確保の観点から、導電性線状体22は疑似シート構造体20において、略等間隔に配列されていることが好ましい。
複合線状体の金属としては、例えば、金、銀、銅、鉄、アルミニウム、ニッケル、クロム、スズ、亜鉛等の金属単体、これら金属単体の少なくとも一種を含む合金(銅-ニッケル-リン合金、銅-鉄-リン-亜鉛合金等)が挙げられる。
導電性線状体22は、金属ワイヤーを含む線状体であってもよい。金属ワイヤーを含む線状体は、1本の金属ワイヤーからなる線状体であってもよいし、複数本の金属ワイヤーを撚った線状体であってもよい。
金属ワイヤーとしては、銅、アルミニウム、タングステン、鉄、モリブデン、ニッケル、チタン、銀、金等の金属、又は、金属を2種以上含む合金(例えば、ステンレス鋼、炭素鋼等の鋼鉄、真鍮、りん青銅、ジルコニウム銅合金、ベリリウム銅、鉄ニッケル、ニクロム、ニッケルチタン、カンタル、ハステロイ、レニウムタングステン等)を含むワイヤーが挙げられる。また、金属ワイヤーは錫、亜鉛、銀、ニッケル、クロム、ニッケルクロム合金、はんだ等でめっきされたものであってもよく、後述する炭素材料やポリマーにより表面が被覆されたものであってもよい。特に、タングステン及びモリブデン並びにこれらを含む合金から選ばれる一種以上の金属を含むワイヤーが、低い体積抵抗率の導電性線状体22とする観点から好ましい。
金属ワイヤーとしては、炭素材料で被覆された金属ワイヤーも挙げられる。金属ワイヤーは、炭素材料で被覆されていると、金属光沢が低減し、金属ワイヤーの存在を目立たなくすることが容易となる。また、金属ワイヤーは、炭素材料で被覆されていると金属腐食も抑制される。
金属ワイヤーを被覆する炭素材料としては、カーボンブラック、活性炭、ハードカーボン、ソフトカーボン、メソポーラスカーボン、カーボンファイバー等の非晶質炭素;グラファイト;フラーレン;グラフェン;カーボンナノチューブ等が挙げられる。
接着剤層30は、接着剤を含む層である。疑似シート構造体20の第二面20B上に接着剤層30を積層したシート10とすることで、接着剤層30により、シート10の被着体への貼り付けが容易となる。なお、接着剤層30は、必要に応じて設けられる層である。シート10は、第一面20Aを被着体に対向させて被着体に接着することができる。この場合には、上述したように、シート10において、疑似シート構造体20から露出する接着剤層30の第一接着面30Aにより、シート10と被着体との接着が容易となる。また、第二接着面30Bを被着体に対向させてシート10を被着体に接着してもよい。
エネルギー線による硬化の条件は、用いるエネルギー線によって異なるが、例えば、紫外線照射により硬化させる場合、紫外線の照射量は、10mJ/cm2~3,000mJ/cm2、照射時間は1秒~180秒であることが好ましい。
なお、当該アクリル系共重合体は、単量体成分(a1’)および単量体成分(a2’)以外のその他の単量体成分(a3’)に由来する構成単位(a3)をさらに含んでいてもよい。
ヒドロキシ基含有モノマーとしては、例えば、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、2-ヒドロキシブチル(メタ)アクリレート、3-ヒドロキシブチル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレート等が挙げられ、2-ヒドロキシエチル(メタ)アクリレートが好ましい。
カルボキシ基含有モノマーとしては、例えば、(メタ)アクリル酸、マレイン酸、フマル酸、イタコン酸等が挙げられ、(メタ)アクリル酸が好ましい。
エポキシ基含有モノマーとしては、例えば、グリシジル(メタ)アクリレート等が挙げられる。
アミノ基含有物モノマーとしては、例えばジアミノエチル(メタ)アクリレート等が挙げられる。
シアノ基含有モノマーとしては、例えばアクリロニトリル等が挙げられる。
エネルギー線硬化性の成分としては、例えばエネルギー線が紫外線である場合には、例えば、トリメチロールプロパントリ(メタ)アクリレート、エトキシ化イソシアヌル酸トリ(メタ)アクリレート、ジトリメチロールプロパンテトラ(メタ)アクリレート、テトラメチロールメタンテトラ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ジペンタエリスリトールモノヒドロキシペンタ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、カプロラクトン変性ジペンタエリスリトールヘキサ(メタ)アクリレート、1,4-ブチレングリコールジ(メタ)アクリレート、1,6-ヘキサンジオールジ(メタ)アクリレート、ジシクロペンタジエンジメトキシジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、オリゴエステル(メタ)アクリレート、ウレタン(メタ)アクリレートオリゴマー、エポキシ変性(メタ)アクリレート、ポリエーテル(メタ)アクリレート等の化合物であって、一分子中に紫外線重合性の官能基を2つ以上有する化合物等が挙げられる。
エネルギー線硬化性の成分は、単独で用いても二種以上を混合して用いてもよい。
硬化性官能基としては、例えば、水酸基、カルボキシル基、アミノ基、グリシジル基、エポキシ基、エーテル基、エステル基、エチレン性不飽和結合を有する基等が挙げられる。これら硬化性官能基を有する化合物としては、例えば、シランカップリング剤等が挙げられる。
エネルギー線硬化性官能基を有する化合物により表面修飾された無機充填材であると、例えば、シート10をガラス等の被着体に貼付けた後に硬化した粘着剤層が強靭となる。これにより、窓および鏡等に貼り付けたシート10に吸盤を貼り付けて、シート10をはがす際等に、硬化後の粘着剤層が破壊することを回避することが容易となる。
なお、粘着剤層が表面修飾された無機充填材を含有する場合には、粘着剤層は、別途エネルギー線硬化性の成分を含んでいることが好ましい。
なお、無機充填材の平均粒径は、デジタル顕微鏡により無機充填材を20個観察し、無機充填材の最大径と最小径の平均径を直径として測定し、その平均値とする。
本実施形態に係るシート10の製造方法は、特に限定されない。シート10は、例えば、次の工程を経て製造される。
まず、剥離シートの上に、接着剤層30の形成用組成物を塗布し、塗膜を形成する。次に、塗膜を乾燥させて、接着剤層30を作製する。次に、接着剤層30の第一接着面30A上に、導電性線状体22を配列しながら配置して、疑似シート構造体20を形成する。例えば、ドラム部材の外周面に剥離シート付きの接着剤層30を配置した状態で、ドラム部材を回転させながら、接着剤層30の第一接着面30A上に導電性線状体22を螺旋状に巻き付ける。その後、螺旋状に巻き付けた導電性線状体22の束をドラム部材の軸方向に沿って切断する。これにより、疑似シート構造体20を形成すると共に、接着剤層30の第一接着面30Aに配置する。そして、疑似シート構造体20が形成された剥離シート付きの接着剤層30をドラム部材から取り出す。この工程を経た後、剥離シートを接着剤層30から剥離することで、シート10が得られる。この方法によれば、例えば、ドラム部材を回転させながら、導電性線状体22の繰り出し部をドラム部材の軸と平行な方向に沿って移動させることで、疑似シート構造体20における隣り合う導電性線状体22の間隔Lを調整することが容易である。
本実施形態に係るシート10の光線透過率は、70%以上が好ましく、70%~100%がより好ましく、80%~100%がさらに好ましい。被着体として自動車等の窓にシート10を貼付する場合、例えば、他の車両、歩行者、信号、標識、および道路の状況等を見分ける視認性が求められる。また、被着体として鏡にシート10を貼付する場合、造影の鮮明性が求められる。このため、シート10の光線透過率が70%以上であれば、これらの視認性、又は造影の鮮明性を容易に得ることができる。
なお、シート10(疑似シート構造体20)の光線透過率は、光線透過率計により、可視域(380nm~760mm)の光線透過率を測定し、その平均値とする。
なお、シート10の面抵抗は、次の方法により測定する。まず、電気的接続を向上させるために、銀ペーストをシート10の擬似シート構造体10の両端に塗布する。その後、銅テープを両端に貼付けたガラス基板に、シート10を銀ペーストと銅テープが接触するように貼付けた後、電気テスターを用いて抵抗を測定し、シート10の面抵抗を算出する。
本実施形態に係るシート10は、例えば、被着体に貼付けて使用される。接着剤層30が硬化性を有する場合、シート10を被着体に貼付けた後、接着剤層30を硬化する。シート10を被着体に貼り合わせる際には、シート10の疑似シート構造体20側を被着体に貼付けて(すなわち、接着剤層30の第一接着面30Aと被着体との間に疑似シート構造体20を介在させて被着体に貼付けて)もよいし、シート10の第二接着面30Bを被着体に貼付けてもよい。
なお、接着剤層30の第一接着面30A側に後述する支持体32が存在しない場合には、シート10の疑似シート構造体20側を、被着体に貼り合わせることが好ましい。被着体および接着剤層30の両方により疑似シート構造体20が十分に保護されるためである。これにより、シート10の耐衝撃性が向上する点で、実用化に適しているといえる。また、シート10(疑似シート構造体20)を発熱体として適用する場合、接着剤層30は、発熱時(通電時)の感電防止にも寄与する。
本実施形態に係るシート10は、上記形態に限定されず、変形、又は改良してもよい。以下、本実施形態に係るシート10の変形例について説明する。以下の説明では、本実施形態に係るシート10で説明した部材と同一であれば、図中に、同一符号を付してその説明を省略または簡略する。
本実施形態に係るシート10は、例えば、図3に示すように、疑似シート構造体20の第一面20A、又は接着剤層30の第二接着面30B上に積層された支持体32を有していてもよい。支持体32を疑似シート構造体20の第一面20A上に積層する場合、シート10において、疑似シート構造体20から露出する接着剤層30の第一接着面30Aにより、支持体32を固定することができる。
なお、図3には、接着剤層30の第二接着面30B上に積層された支持体32を有するシート11が示されている。
なお、接着剤層30又は疑似シート構造体20とは対向しない支持体32の表面(シート10から露出する表面)には、シート10(疑似シート構造体20)の保護性を強化するために、紫外線硬化性樹脂等を用いたハードコート処理等が施されていてもよい。
本実施形態に係るシート10は、例えば、疑似シート構造体20の第一面20A、及び接着剤層30の第二接着面30Bの少なくとも一方の面上に積層された剥離層34を有してもよい。
なお、図4には、疑似シート構造体20の第一面20A、及び接着剤層30の第二接着面30Bの双方の面上に積層された剥離層34を有するシート12が示されている。
剥離基材としては、例えば、紙基材、紙基材等に熱可塑性樹脂(ポリエチレン等)をラミネートしたラミネート紙、プラスチックフィルム等が挙げられる。紙基材としては、グラシン紙、コート紙、キャストコート紙等が挙げられる。プラスチックフィルムとしては、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート等のポリエステルフィルム;ポリプロピレン、ポリエチレン等のポリオレフィンフィルム等が挙げられる。剥離剤としては、例えば、オレフィン系樹脂、ゴム系エラストマー(例えば、ブタジエン系樹脂、イソプレン系樹脂等)、長鎖アルキル系樹脂、アルキド系樹脂、フッ素系樹脂、シリコーン系樹脂等が挙げられる。
剥離層34の剥離剤層の厚さは、特に限定されない。剥離剤を含む溶液を塗布して剥離剤層を形成する場合、剥離剤層の厚さは、0.01μm~2.0μmが好ましく、0.03μm~1.0μmがより好ましい。
剥離基材としてプラスチックフィルムを用いる場合、プラスチックフィルムの厚さは、3μm~150μmであることが好ましく、5μm~100μmであることがより好ましい。
本実施形態に係るシート10は、例えば、図5に示すように、疑似シート構造体20の第一面20A上に積層された他の接着剤層31を有するシート13であってもよい。つまり、本実施形態に係るシート10は、疑似シート構造体20の両面(第一面20A及び第二面20B)に接着剤層を有してもよい。
接着剤層30と接着剤層31との厚さは、各々、3μm~150μmであることが好ましく、5μm~100μmであることがより好ましい。また、接着剤層30と接着剤層31との厚さの合計値(接着剤層の総厚さ)は、10μm~300μmが好ましく、20μm~200μmであることがより好ましい。
本実施形態に係るシート10は、例えば、図6に示すように、接着剤層30の第二接着面30B上に支持層36を介して積層された他の接着剤層31を有するシート14であってもよい。つまり、本実施形態に係るシート10は、疑似シート構造体20の第二面20Bに、支持層36を介して積層された一対の接着剤層30,31を含む接着シート(両面テープ等)を有していてもよい。
支持層36としては、例えば、紙、熱可塑性樹脂フィルム、硬化性樹脂の硬化物フィルム、金属箔、ガラスフィルム等が挙げられる。熱可塑性樹脂フィルムとしては、例えば、ポリエステル系、ポリカーボネート系、ポリイミド系、ポリオレフィン系、ポリウレタン系、アクリル系等の樹脂フィルムが挙げられる。
本実施形態に係るシート10は、例えば、図7に示すように、疑似シート構造体20の導電性線状体22が周期的に湾曲又は屈曲していてもよい。具体的には、導電性線状体22は、例えば、正弦波、矩形波、三角波、のこぎり波等の波形状であってもよい。つまり、疑似シート構造体20は、例えば、一方に延びた波形状の導電性線状体22が、導電性線状体22の延びる方向と直交する方向に、等間隔で複数配列された構造としてもよい。
なお、図7は、一方に延びた波形状の導電性線状体22が、導電性線状体22の延びる方向と直交する方向に、等間隔で複数配列された疑似シート構造体20を有するシート15が示されている。
本実施形態に係るシート10は、例えば、図8に示すように、疑似シート構造体20を複数積層した積層体を有するシートであってもよい。複数の疑似シート構造体20は、互いの導電性線状体22を平行に積層してもよいし、交差させて積層させてもよい。一方の疑似シート構造体20において平行に配列され、交わることのない導電性線状体22同士が、他方の疑似シート構造体20の導電性線状体22によっていわば橋渡しされ、これらの間の電気的な接続を生じさせることができる観点からは、互いの導電性線状体22を交差させて積層させることが好ましい。
ここで、一方の疑似シート構造体20における導電性線状体22が、他方の擬似シート構造体20における間隙部分(隣り合う導電性線状体22同士の間隔の部分)と重なり、間隙部分が塞がれることによって、光線透過性が低下する可能性があるが、L/Dの値を上述した範囲内で調整することで、容易に十分な光線透過性を確保することができる。
なお、図8には、互いの導電性線状体22を交差させて、2つの疑似シート構造体20を積層したシート16が示されている。
本実施形態に係るシート10は、例えば、図9に示すように、疑似シート構造体20をシート面方向(シート表面に沿った方向)に複数配列したシートであってもよい。複数の疑似シート構造体20は、互いの導電性線状体22を平行に配列してもよいし、交差させて配列させてもよい。
なお、図9には、互いの導電性線状体22を平行に配列させて、2つの疑似シート構造体20を配列したシート17が示されている。
本実施形態に係るシート10は、接着剤層30を有さない形態であってもよい。シート10は、例えば、疑似シート構造体20が、少なくとも複数の導電性線状体22の端部が固定部材により固定され、かつ固定された複数の導電性線状体22の端部以外に、他の部材と接触していない独立した部分を有する形態であってもよい。具体的には、シート10は、例えば、図10に示すように、疑似シート構造体20の縁部が固定部材38(例えば、両面テープ、芯材を有さず、単層の接着剤からなる両面接着性の膜、半田、ヒートシール性のフィルム、クリップや万力等の挟み具等の固定部材)により固定された疑似シート構造体20からなるシート18(フリースタンディング状態のシート)であってもよい。
なお、疑似シート構造体20の縁部が固定部材38により固定された形態に限られず、疑似シート構造体20の対向する一対の縁部のみ(複数の導電性線状体22の端部のみ)が固定部材38により固定された形態であってもよい。
本実施形態に係るシート10は、光線透過性が高く、かつ面抵抗が低い疑似シート構造体を有するため、発熱体として適用することが好適である。つまり、本実施形態に係るシート10からなる発熱体(本実施形態に係る発熱体)は、光線透過性が高く、かつ印加する電圧の低減が可能な発熱体となる。
そして、本実施形態に係る発熱装置40としては、例えば、浴室等の鏡;乗用車、鉄道、船舶、航空機等の輸送用装置の窓;建物の窓;アイウェア等に配置されるデフォッガー(defogger)、輸送用装置の窓、信号機の点灯面、標識等に配置されるデアイサー(deicer)等が挙げられる。
キャリアガスとしてアルゴンガス、炭素源としてアセチレン、蒸着装置として3つの炉を備える熱CVD(Chemical Vapor Deposition)装置を用い、触媒CVD法により、幅50mmのシリコンウエハ上にカーボンナノチューブフォレストを得た。
カーボンナノチューブフォレストの端部の一部をつまみ、カーボンナノチューブシートを幅7mmで引き出した。このカーボンナノチューブシートを直径5mmの金属製の輪を通して、シートが束ねられるようにし、束ねられたシートを直径3cmのゴムドラム上に当て、ゴムドラムをドラムの軸方向に振動運動させて、束ねられたシートがゴムドラム上を摺動するようにした。この摺動において発生する摩擦により、束ねられたシートがリボン状に撚られるようにした。この状態で、リボン状の線状体をボビンに巻き付けていき、フォレストからシートの引き出し、シートの集束、束の撚り、及びリボン状の線状体の巻取りを連続して行った。
カーボンナノチューブシートの線状体の代わりに、金属ワイヤーからなる線状体(金属種:Stainless Steel、品番:AISI 316L(Good fellow社製)、直径:50μm)を用いた以外は、実施例1と同様にして、粘着シートに金属ワイヤーからなる線状体が配列した疑似シート構造体が積層されたシートを得た。疑似シート構造体の金属ワイヤーからなる線状体の直径D及び間隔Lについて、既述の方法により測定したところ、金属ワイヤーからなる線状体の直径Dは50μm、配列した金属ワイヤーからなる線状体の間隔Lは1700μmであった。
ゴムドラムが移動する速度をより遅く変化させて、線状体を巻き付けた以外は、実施例1と同様にして、粘着シートにカーボンナノチューブの線状体が配列した疑似シート構造体が積層されたシートを得た。疑似シート構造体の線状体の直径D及び間隔Lについて、既述の方法により測定したところ、線状体の直径Dは20μm、配列した線状体の間隔Lは800μmであった。
ゴムドラムが移動する速度をより遅く変化させて、線状体を巻き付けた以外は、実施例1と同様にして、粘着シートにカーボンナノチューブの線状体が配列した疑似シート構造体が積層されたシートを得た。疑似シート構造体の線状体の直径D及び間隔Lについて、既述の方法により測定したところ、線状体の直径Dは20μm、配列した線状体の間隔Lは200μmであった。
ゴムドラムが移動する速度をより遅く変化させて、線状体を巻き付けた以外は、実施例1と同様にして、粘着シートにカーボンナノチューブの線状体が配列した疑似シート構造体が積層されたシートを得た。疑似シート構造体の線状体の直径D及び間隔Lについて、既述の方法により測定したところ、線状体の直径Dは20μm、配列した線状体の間隔Lは10μmであった。
ゴムドラムが移動する速度をより速く変化させて、線状体を巻き付けた以外は、実施例1と同様にして、粘着シートにカーボンナノチューブの線状体が配列した疑似シート構造体が積層されたシートを得た。疑似シート構造体の線状体の直径D及び間隔Lについて、既述の方法により測定したところ、線状体の直径Dは20μm、配列した線状体の間隔Lは10000μmであった。
カーボンナノチューブシートの線状体の直径を20μmに代えて15μmとし、かつゴムドラムが移動する速度をより遅く変化させて線状体を巻き付けた以外は、実施例1と同様にして、粘着シートにカーボンナノチューブの線状体が配列した疑似シート構造体が積層されたシートを得た。疑似シート構造体の線状体の直径D及び間隔Lについて、既述の方法により測定したところ、線状体の直径Dは15μm、配列した線状体の間隔Lは100μmであった。
カーボンナノチューブシートの線状体の代わりに金属ワイヤーからなる線状体(金属種:Stainless Steel、品番:AISI 316L(Good fellows社製)、直径:50μm)を用い、かつゴムドラムが移動する速度をより速く変化させて金属ワイヤーからなる線状体を巻き付けた以外は、実施例1と同様にして、粘着シートに金属ワイヤーからなる線状体が配列した疑似シート構造体が積層されたシートを得た。疑似シート構造体の線状体の直径D及び間隔Lについて、既述の方法により測定したところ、金属ワイヤーからなる線状体の直径Dは50μm、配列した金属ワイヤーからなる線状体の間隔Lは5000μmであった。
カーボンナノチューブシートの線状体の代わりに金属ワイヤーからなる線状体(金属種:タングステン、製品名:TGW-B(トクサイ社製)、直径14μm)を用いた以外は、実施例1と同様にして、粘着シートに金属ワイヤーからなる線状体が配列した疑似シート構造体が積層されたシートを得た。疑似シート構造体の線状体の直径D及び間隔Lについて、既述の方法により測定したところ、金属ワイヤーからなる線状体の直径Dは14μm、配列した金属ワイヤーからなる線状体の間隔Lは1700μmであった。
[実施例8]
カーボンナノチューブシートの線状体の代わりに、金属ワイヤーからなる線状体(金属種:モリブデン、製品名:TMG-BS(トクサイ社製)、直径25μm)を用いた以外は、実施例1と同様にして、粘着シートに金属ワイヤーからなる線状体が配列した疑似シート構造体が積層されたシートを得た。疑似シート構造体の金属ワイヤーからなる線状体の直径D及び間隔Lについて、記述の方法により測定したところ、金属ワイヤーからなる線状体の直径Dは25μm、配列した金属ワイヤーからなる線状体の間隔Lは、1700μmであった。
各例で得られたシートの疑似シート構造体について、線状体の体積抵抗率R、線状体の直径D、線状体の間隔Lを既述の方法に従って、測定した。また、各例で得られたシートの光線透過率及び面抵抗について、既述の方法に従って、測定した。結果を表1に示す。
なお、表1中、「直径D」及び「間隔L」の欄において、括弧内の数値は、単位cmの値を示している。そして、「L×D」及び「(D2/R)×(1/L)」の欄の値は、「直径D」及び「間隔L」がcm単位としたときの値を示している。
本明細書に記載された全ての文献、特許出願、および技術規格は、個々の文献、特許出願、および技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。
Claims (11)
- 体積抵抗率Rが1.0×10-7Ωcm~1.0×10-1Ωcmであり、かつ一方向に延びた複数の線状体が、互いに平行に間隔をもって配列された疑似シート構造体を有し、
前記線状体の直径Dと隣り合う前記線状体の間隔Lとの関係が、式:L/D≧3を満たし、
かつ前記線状体の直径Dと隣り合う前記線状体同士の間隔Lと前記線状体の体積抵抗率Rとの関係が、式:(D2/R)×(1/L)≧0.003(式中のDおよびLの単位はcmである)を満たすシート。 - 前記線状体が、カーボンナノチューブを含む線状体である請求項1に記載のシート。
- 前記線状体が、カーボンナノチューブを含み、かつ直径が1μm~125μmの線状体である請求項1に記載のシート。
- 前記線状体が、カーボンナノチューブと金属とを含む線状体である請求項1~請求項3のいずれか1項に記載のシート。
- 前記疑似シート構造体が積層される接着剤層を有する請求項1~請求項4のいずれか1項に記載のシート。
- 前記疑似シート構造体が複数重ねられた積層体を有する請求項1~請求項5のいずれか1項に記載のシート。
- 前記疑似シート構造体が、少なくとも前記複数の線状体の端部が固定部材により固定され、かつ固定された前記複数の線状体の端部以外に、他の部材と接触していない独立した部分を有する請求項1~請求項6のいずれか1項に記載のシート。
- 請求項1~請求項7のいずれか1項に記載のシートからなる発熱体。
- 請求項8に記載の発熱体と、前記発熱体に給電する給電部とを有する発熱装置。
- デフォッガーである請求項9の発熱装置。
- デアイサーである請求項9に記載の発熱装置。
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CN201680067220.3A CN108430755B (zh) | 2015-11-20 | 2016-11-17 | 片材、发热体、及发热装置 |
JP2017514382A JP6178948B1 (ja) | 2015-11-20 | 2016-11-17 | シート、発熱体、及び発熱装置 |
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